Resin made from tannin, sulfuric acid, acetone, and potassium cyanide



Patented Mar. 25, 1952 OFFICE RESIN'MADE. FROM TANNIN, SULFUBIC', ACID,ACETQNE, AND POTASSIUM CY-v Vinicio Da Veiga, Sac; Paulo, Brazil NoDrawing, Application April 27-, 1948, Serial No. 23,616

' 17Claims. 1 V

This invention relates; to plastic synthetic resins, and to the processof manufacture therefor- It is an object of; the invention to produce asynthetic resin which may be translucent, and which is capable of, beingmoulded, for industrial purposes, in, accordance with usual; practice,or by special; procedures. andv appar u Itv isan, object of theinvention to produce a substantially translucent synthetic resin whichmay beprocessed into sheet form of any desired k ess. Such mater almaybe e the hard flexible. and, nerally will... by reason. oi prop r.-t-ies suchasitslightness andtranslucency, be desirable, as a substitutefor glass.

It, is. auobj'ect oi the inventionvto, prov a process for the productionof asynthetic, resin of reatstren th, no brit laan ha a favorablereaction to high and low temperatures...

It is an object of the invention to provide a synthetic resinfor theproduction of which simple apparatus and materials commonly availablecan be used.

It is an object of the invention toprovid'e a synthetic resin, and theprocess for the manufacture of such a product, which, in the form ofsheets, is capable of being cut or sawed in the cold state, or of beingnai1ed, 01' in thin sheet form of being sewn, or of being bonded tomaterials such as iron,v steel, silver, gold, and other metals.

The product of the process in accordance with the invention may bemelded, at a temperature around 13Q C., into various forms. In sheetform,,it can be processed into articles of clothing and various otherarticles.

It is an object of; the invention to provide a synthetic resin theprocess for the production of which involves very simple apparatus, andthe production of which is efiected in a period of time much shorterthan that presently consumed for the preparation of other syntheticresins.

Other objects of this invention will be set forth hereinafter, or willbe apparent from, the description wherein certain embodiments forcarrying out the invention are exemplified.

The invention, however, is not intended te be restricted to anyparticular composition, or any particular proportion, or any particularapplica: tion of any such composition, or proportion, or any particularprocess of preparation, or method of use, or, any of. various detailsthereon, even whe le specifically described herein, as the same may bmod fied n. va ious p iculars or may be applied in many varied relationswithout. de-

parting from the spirit an scope. of the claimed invention, of which,the exemplifying embodiments, herein described, are intended only to beillustrative, and only: for the purpose of complying with therequirements of the statutes for dis-- closure of an operative.embodiment, but not to demonstrate all; the various modifications inwhich the invention might be embodied.

Forcarrying out the invention, the process may follow any one of a,number of different procedures. In one. case, the. process so far as theproduction of the monomer, before polymerization, is concerned is;carried out in a single vessel. Atvarious, sta es, that. vesselv issealed, and functions as a pressure chamber. At other times, it mayfunctiorr as a. refluxing distillation apparatus. The vessel is suitablyconstructed to avoid corrosion, in view of the ingredients used. A leadlining has. been found necessary for that purpose. The vesseli isprovided with means to efiect agitation of the material being processedcontinuously therein. For instance, stirrers may be mounted with thecover of the vessel, and suitable; motorsmay be provided to drive thestirrers. Shafts for the stirrers may extend through stuffing boxes inthe-cover of the vessel. Agitation is intended to occur continuously asthe reaction mixture is heated.

For comparison. purposes only, the process will be described asifit-isbeingv carried out in a vessel having a capacity of approximatelyone liter. Into this vessel are introduced the various ingredients,commencing with sulphuric acid and tannin. The best results have beenobtained by providing the ingredients in the proportions to beindicated; but, of course, it is understood that these proportions maybevaried, and still encompass the principles of the invention. Forinstance, sulphuric acid to the amount of grams, of a concentration of9'7 approximating 81.5 c. c., is delivered into the vessel. To this isadded about 2 grams of tannin. Then the vessel issealed off, agitationis commenced, and the contents heated to -a temperature of 180 C. forone hour.

Now acetone, to the amount of 78 grams at a concentration of 96.5%, isdelivered into the vessel, and potassium cyanide, to the amount of 42grams, is added. The vessel is again sealed ofi', agitation is resumed,and the vessel again is heated, now to a temperature in the rangebetween1 60 C. and Q.

Preferably the vessel is constructed so that the progress of; thereaction, as it proceeds, may be studied. For this purpose, a sighthole, or other means, may be provided. This portion of the reaction isexothermic, and also, after heating has proceeded, gases are given off,resulting in frothing or foaming When this stage is reached, a suitabledischarge vent from the vessel to the atmosphere is opened, and thegases thus being formed released to the atmosphere.

After the reaction has subsided substantially, the vent to theatmosphere is closed, and heating is continued. Agitation has continuedthroughout this stage. The temperature to which the mixture is nowheated is reduced to around 125 C., at which temperature the reaction ismaintained for about 1 to 2 hours. At the end of this period of about 2hours, the vessel is cooled to room temperature. Cooling may be effectedby permitting the vessel to stand, orit'may be accelerated bycirculating a. cooling fluid through coils around the vessel After thevessel has been cooled, alcohol is delivered into the vessel. Methylalcohol is preferred; about 56.05 grams of a concentration of 71.5% isadded. At this time, the balance of tannin is restored by adding about0.03 gram of tannin.

The vessel is sealed off again; agitation is resumed; esterification nowtakes place, as agitation is resumed, and the vessel is heated for'aboutfive hours. The temperature is maintained in a range approximatelybetween 93 C. and 95 C.

After heating for about five hours in this man ner, hydroquinone, to theamount of about 0.025 grams, is added to the product now in thevessel,in order to inhibit polymerization during the ensuing processing. Thevessel is now connected so that a reflux condenser will return thevaporizable ingredients of the reaction, and the mixture in the vesselis heated and agitated. This refluxing is carried on at a temperature inthe range between 85 C. and 140 C., and for about one hour.

After this refluxing stage has been completed, the product left in thevessel is a viscous, syrupy mass. Approximately the same quantity asbefore of hydroquinone, that is, 0.025 grams, is added to this reactionproduct, and about one gram of sodium carbonate is added together withthe wash water, to neutralize any acid which may be present. The washwater is separated from the reaction product by any suitable method. Itmay .be drawn off or siphoned off. Washing is repeated a number oftimes. Each washing may be effected with about 85 c. c. of water and0.45

grams of sulphuric acid to bring the product to a neutral condition. V

The reaction product should now be clear, and

not clouded. If this washing does not produce the proper result, about 3c. c. of ammoniumsulphate is added in order to produce clarification.

Now to this reaction product, 1.85 cc. of commercial liquid phenoltogether with 0.25 grams of hydroquinone, is added. Agitation iscommenced again, and again refluxing ensues, this time at a temperaturein the range between 95 C. and

101 C. After the completion of this refluxing, the product should not beacid. If it is acid, washing is repeated until the product no longer isacid. The final reaction product at this stage is the monomer, which, inthe further processing,

is to be polymerized. This end product is to be 1 by weight of thereaction product. The

mixture is agitated and heated between 93 C. and 95 C. for about onehour. After cooling, there results a crystalline mass which can bepulverized with or without the addition of a plasticizer. Thepulverization may be done in a ball mill. The result is a moldingmaterial which may be molded in the usual manner, in molds at atemperature of around 130 C.

Example II.With 10 parts of the reaction product, 2 parts of butylphthalate, and benzoyl peroxide, to the amount of 1% by weight of thereaction product, are added. Polymerization takes place on standing, orin molds. If polymerizationtakes place merely by standing, the endproduct will be reached in around twelve hours. Where the mass ofpolymerized material is not molded as a part of the step ofpolymerization, it may be pulverized, and thereafter molded in the samemanner as given in connection with Example 1.

Example III.-To 10 parts of the powder resulting from either Example Ior Example II, there is mixed 6 parts of benzoyl peroxide. To thisproduct is added traces of beryllium oxide. This is heated in molds atC. under pressure of about two tons per square foot. The product has theappearance of porcelain.

Example IV.To 250 grams of the product in Examples I or II, 1500 gramsof petroleum jelly or a good mineral oil is added. Then 10 grams 'ofbutyl phthalate from 0.04 gram of benzoyl peroxide are added to make themixture. This mixture is then heated for 50 to 60 minutes in thetemperature range between 93 C. and 95 C. The result is a syrup which isprocessed to eliminate the oil. This may be done by pressing the massbetween rotating rolls. The polymerized material passes through, and theoil is squeezed out and runs off. The material is passed and repassedthrough the'rolls a sufficient number of times to complete removal ofthe oil. The polymerized material is then washed with benzoyl. Theproduct is put in a chamber and heated to C. for six hours. Theresultant product can be molded.

All of these products are clear and translucent. The product of ExampleIV is especially useful in molding teeth. I

Example V.-To the powder produced by Example IV, there is added 1.25parts of beryllium oxide or titanium oxide in relation to about 1000parts of the powder. Pigments are added with 1% of benzoyl peroxide.This massis pulverized again in a ball mill. The end product is usefulfor molding to make dentures and false teeth.

Many other changes could be effected in the particular composition, andin. the proportions thereof, hereinbefore set forth, and in the methodof preparation and use set forth, and in specific details thereof,without substantially departing from the invention defined in theclaims, the specific description being merely of embodiments capable ofillustrating certain principles of the invention.

What is claimed as new and useful is:

1. The steps of heating in a closed vessel with 78 parts by weight ofacetone and 42 parts by weight of cyanide of potassium the product ofdigesting 2 parts of tannin by weight in 150 parts by weight ofconcentrated sulphuric acid, and then adding sufficient tannin torestore the tannin to the amount originally present.

2. The steps of agitating and heating to a temperature of about C. andin a closed vessel with '78 parts by weight of acetone and 42 parts byweight of cyanide or potassium the product of digesting 2 parts by-we'igl-it of tannin in 150 parts by weight of concentrated sulphuricacid,

dissipating the evolved gases, and thereafter heating and agitating thereaction product at about 125 C. and under pressure, and then adding:sufiicient tannin to restore the tannin to the amount originallypresent.

3. The'step's "of heating with 78 parts by weight of acetone and 42parts by weight 'of potassium cyanide for about twohours at about 170 C.The product of digesting '2 parts by weight of tannin and 1 50 parts byweight of sulphuric acid, cooling the product, and then addingsufficient tannin to restore thetannin to the amount originally present,and adding about 56 parts by weight of methyl alcohol, and then heating.

4. The steps of heating with '78 parts by weight of acetone and 42 partsby weight of potassium cyanide for about "two hours at about 170 C. Theproduct of digesting 2 parts by weight of tannin and 150 parts by weightofsu'lphuric acid, cooling the product, and then adding 's'u-flicienttannin to restore the tannin to the amount originally present, andadding about 56 parts by weight of methyl alcohol, then heating for'about'five hours at a temperature of about 95 and refluxing the productbetween the limits of 85 and 140 C. in the presence of traces ofhydroquinone.

5. The steps of heating with 78 grams of acetone and 42 :gramsofpotassium cyanide for about two hours at about 170 C. the product ofdigesting 2 grams of tanninand 150 grams of sulphuric acid, cooling theproduct, and then adding suflicient tannin to restore the tannin to theamount originally present, and adding about 56 grams of methyl alcohol,then heating for about flve hours at a temperature of about 95 C.,refluxing the product between the limits of 85 and 140 C. in thepresence of traces of hydroquinone, washing the product to asubstantially neutral condition, adding about 1.85 cubic centimeters ofliquid phenol, and refluxing the product between 95 and 101 C.

6. The steps of polymerizing the monomer produced by the process ofclaim 5 by mixing the monomer with butyl phthalate and benzoyl .per-

oxide, and pouring the mi-x-tureinto molds.

.7. The steps of polymerizing the-monomer produced by the process ofclaim '5 by mixing the monomer with mineral oil, butyl phthalate andbenzoyl peroxide, heating the mixture, and eliminating the oil from themixture by squeezing the mixture.

8. The product produced by the process comprising the step of agitatingand heating under pressure to a temperature of about 170 C. and withoutaccess of air the product of digesting 2 parts by weight of tannin-H1150parts by weight of concentrated sulphuric acid, and then adding 78 partsby weight of acetone and 42 parts by weight of cyanide of otassium.

9. The reaction product of a process "which includes heating for abouttwo hours at about 170 C. with 78 arts by weight of acetone and 42 partsby weight of potassium cyanide the prodnot of digesting 2 parts by-weight of tannin and 150 parts by Wlght (if sulphuric acid, addingtannin and methyl alcohol, continuing heating, refluxing the product inthe presence 'O'f traces of hydroduinon'e, washing the product to asubstantially neutral condition, adding phenol, and heating.

10. The process or preparing a roduct for polymerization to produce aplastic resin, ineluding the Steps OT agitating if! a Scaled (Bimtain'er and ata temperature of about 180 C. for one hour sulphuric acidand tannin in a batch having approximately the proportions of 150 gramsof 97%'% sulphuric acid to two grams of tannin, adding acetone andpotassium cyanide to the resultant product in the proportion of 78 gramsof 96.5% acetone to 42 grams ofpotassium cyanide, then agitating andmaintaining the temperature between 160 C. and 170 C., venting to theatmosphere evolved gases, agitating after subsidence of gas evolutionand maintaining the temperature at about 125 C. for a period of about'on and one-half hours to two hours, cooling the reaction product,agitating the product with methyl alcoholand tannin in the proportionsof 5605 grams of 71.5% methyl alcohol and 0.03 grams of tannin, andheating the mixture for about iflve hours between 93 C. and 95 CL;adding hydroquinone in the proportion of 0.025 grams to the stageproduct, and refluxing the resultant mixture while agitating it byheating it to a tem-- perature between C. and 140 C. for about one hour;adding hydroquinone in the proportion of 0.025 gram to the step product,washing, neutralizing and clarifying the step product; adding commercialliquid phenol and hydroquinone in the proportions of 1.85 c. c. ofphenol and 0.25 grams of hydroquinone, refluxing while agitating andheating betwee'nthe temperatures of 'C. and 101 C., and washing toremove any acidity.

11. The process of preparing a plastic resin, including the steps ofagitating in a sealed container and at "a temperature of about 180 C.for one hour sulphuric acid and tannin in a batch having approximatelythe proportions of 150.

grams of 97 sulphuric acid to two grams of tannin, adding acetone andpotassium cyanide to the resultant product in the proportion of 78 gramsof 96.5% acetone to 42 grams of potassium cyanide, then agitating andmaintaining the temperature between 160 C. and 170 C., venting to theatmosphere evolved gases, agitating after subsidence of gas evolutionand maintaining the temperature at about C. for a period of about oneand one-half hours to two hours, cooling the reaction product, agitatingthe product with methyl alcohol and tannin in the proportions of 56.05grams of 71.5% methyl alcohol and 0.03 gram of tannin, and heating themixture for about five hours between 93 C. and 95 C.; addinghydroquinone in the proportion of 0.025 grain to the stage product, andrefluxing the resultant mixture while agitating it by heating it to atemperature between 85 C. and C. for about one hour; adding hydroquinonein the proportion of 0.025 gram to the step product, washing,neutralizing and clarifying the step product; adding commercial liquidphenol and hydroquinone in the proportions of 1.85 c. c. of phenol and0.25 gram of hydroquinone, refluxing while agitating and heating betweenthe temperatures of 95 C. and 101 C., washing to remove any acidity;mixing with the final reaction product benzoyl peroxide in the amount of10% by weight of the final reaction product, and agitating the mixtureand heating it between 93 C. and 95 C. for about one hour.

12. The process of preparing a plastic resin, including the steps ofagitating in a sealed contain er and at a temperature of about 180 C.for one hour sulphuric acid and tannin in a batch having approximatelythe proportions of grams of 97 sulphuric acid to two grams of tannin,adding acetone and potassium cyanide to the resultant product in theproportion of 78 grams of 96.5% acetone to 42 grams of potassiumcyanide, then agitating and maintaining the temperature between 160 C.and 170 C., venting to the atmosphere evolved gases, agitating aftersubsidence of gas evolution and maintaining the temperature at about 125C. for a period of about one and one-half hours to two hours, coolingthe reaction product, agitating the product with methyl alcohol andtannin in the proportions of 56.05 grams of 71.5% methyl alcohol and0.03 gram of tannin, and heating the mixture for about five hoursbetween 93 C. and 95 0.; adding hydroquinone in the proportion of 0.025gram to the stage product, and refluxing the resultant mixture whileagitating it by heating it to a temperature between 85 C. and 140 C. forabout one hour; adding hydroquinone in the proportion of 0.025 gram tothe step product, washing, neutralizing and clarifying the step product;adding commercial liquid phenol and hydroquinone in the proportions of1.85 cc. of phenol and 0.25 gram of hydroquinone, refluxing whileagitating and heating between the temperatures of 95 C. and 101 0.,washing to remove any acidity; mixing the final reaction product withbutyl phthalate and benzoyl peroxide in the proportions of ten parts ofthe reaction product, two parts of butyl phthalate and benzoyl peroxidein the amount of 1% by weight of the reaction product, and permittingthe mixture to stand.

13. The process of preparing a plastic resin, including the steps ofagitating in a sealed container and at a temperature of about 180 C. for

one hour sulphuric acid and tannin in a batch having approximately theproportions of 150 grams of 97 /2% sulphuric acid to two grams oftannin, adding acetone and potassium cyanide to the resultant product inthe proportion of 78 grams of. 96.5% acetone to 42 grams of potassiumcyanide, then agitating and maintaining the temperautre between 160 C.and 170 C., venting to the atmosphere evolved gases, agitating aftersubsidence of gas evolution and maintaining the temperature at about 125C. for a period of about one and one-half hours to two hours, coolingthe reaction product, agitating the product with methyl alcohol andtannin in the proportions of 56.05 grams of 71.5% methyl alcohol and0.03 gram of tannin, and heating the mixture for about five hoursbetween 93 C. and 95 0.; adding hydroquinone in the proportion of 0.025grams to the stage product, and refluxing the resultant mixture whileagitating it by heating it to a tem-- perature between 85 C. and 140 C.for about one hour; adding hydroquinone in the proportion of 0.025 gramto the step product, washing, neutralizing and clarifying the stepproduct; adding commercial liquid phenol and hydroquinone in theproportions of 1.85 cc. of phenol and 0.25 gram of hydroquinone,refluxing While agitating and heating between the temperatures of 95 C.and 101 C., washing to remove any acidity; mixing with the finalreaction product benzoyl peroxide in the amount of 10% by weight of thefinal reaction product, agitating the mixture and. heating it between 93C. and 95 C. for about one hour; pulverizing the final step product,adding traces of beryllium oxide and benzoyl peroxide to the resultantpowder in the proportions of six parts of benzoyl peroxide to ten partsof the powder, depositing the resultant mixture in molds, and heatingthe mixture in the molds at 140 C. fancll under pressure of about twotons per square 14. The process of preparing a plastic resin, includingthe steps of agitating in a sealed container and at a temperature ofabout 180 C. for one hour sulphuric, acid and tannin in a batch havingapproximately the proportions of 150 grams of 97 sulphuric acid to twograms of tannin, adding acetone and potassium cyanide to the resultantproduct in the proportion of 78 grams of 96.5% acetone to 42 grams ofpotassium cyanide, then agitating and maintaining the temperaturebetween 160 C. and 170 C., venting to the atmosphere evolved gases,agitating after subsidence of gas evolution and maintaining thetemperature at about 125 C. for a period of about one and one-half hoursto two hours, cooling the reaction product, agitating the product withmethylalcohol and tannin in the proportions of 56.05 grams of 71.5%methyl alcohol and 0.03 grams of tannin, and heating the mixture forabout five hours between 93 C. and 95 0.; adding hydroquinone in theproportion of 0.025 grams to the stage product, and refluxing theresultant mixture while agitating it by heating it to a temperaturebetween C. and 140 C. for about one hour; adding hydroquinone in theproportion of 0.025 gram to the step product, washing, neutralizing andclarifying the step product; adding commercial liquid phenol andhydroquinone in the proportions of 1.85 cc. of phenol and 0.25 gram ofhydroquinone, refluxing while agitating and heating between thetemperatures of C. and 101 C., washing to remove any acidity; mixing thefinal reaction product with butyl phthalate and benzoyl peroxide in theproportions of ten parts of the reaction product, two parts of butylphthalate and benzoyl peroxide in the amount of 1% by Weight of thereaction product, permitting the mixture to stand; pulverizing the finalstep product, adding traces of beryllium oxide and benzoyl peroxide tothe resultant powder in the proportion of six parts of benzoyl peroxideto ten parts of the powder, depositing the resultant mixture in molds,and heating the resultant mixture in the molds at C. and under pressureof about two tons per square foot.

15. The process of preparing a plastic resin, including the steps ofagitating in a sealed container and at a temperature of about 180 C. forone hour sulphuric acid and tannin in a batch having approximately theproportions of grams of 97 sulphuric acid to two grams of tannin, addingacetone and potassium cyanide to the resultant product in the proportionof 78 grams of 96.5% acetone to 42 grams of potassium cyanide, thenagitating and maintaining the temperature between C. and C., venting tothe atmosphere evolved gases, agitating after sub sidence of gasevolution and maintaining the temperature at about 125 C. for a periodof about one and one-half hours to two hours, cooling the reactionproduct, agitating the product with methyl alcohol and tannin in theproportions of 56.05 grams of 71.5% methyl alcohol and 0.03 grams oftannin, and heating the mixture for about five hours between 93 C. and95 0.; adding hydroquinone in the proportion of 0.025 grams to the stageproduct, and refluxing the resultant mixture while agitating it byheating it to a temperature between 85 C. and 140 C. for about one hour;adding hydroquinone in the proportion of 0.025 gram to the step product,washing, neutralizing and clarifying the step product; adding commercialliquid phenol and hydroquinone in the proportions of 1.85 c. c. ofphenol and 0.25 grams of hydroquinone for each batch, refluxing whileagitating and heating between the temperatures of 95 C. and 101 0.,washing to remove any acidity; mixing with the final reaction productbenzoyl peroxide in the amount of by weight of the final reactionproduct, agitating the mixture and heating it between 93 C. and 95 C.for about'one hour; mixing with the final reaction product a productselected from the group consisting of petroleum jelly and mineral oil inone proportions of 250 parts of product and 1500 parts of the petroleumproduct, adding butyl phthalate and benzoyl peroxide to the resultantmix in the proportions of 10 grams of butyl phthalate and 0.04 gram ofbenzoyl peroxide for each 250 grams of final reaction product, heatingthe mix for about to minutes between 93 C. and 95 C., expressing andwashing the petroleum product from the heated mix, and heating thepetroleum-expressed residue in a chamber for about six hours at 160 C.

16. The process of preparing a product for polymerization to produce aplastic resin, including the steps of agitating in a sealed containerand at a temperature of about 180 C. for one hour su1phuric acid andtannin in a batch having approximately the proportions of grams ofconcentrated sulphuric acid to about two grams of tannin, adding acetoneand potassium cyanide to the resultant product in the proportions ofabout '78 grams of 96.5% acetone to about 42 grams of potassium cyanide,and then agitating and maintaining the temperature between C. and C.

17. The process of preparing a product for polymerization to produce aplastic resin, including the steps of agitating in a sealed containerand at a temperature of about C. for one hour sulphuric acid and tanninin a batch having approximately the proportions of 150 grams ofconcentrated sulphuric acid to about two grams of tannin, adding acetoneand potassium cyanide to the resultant product in the proportions ofabout '78 grams of 96.5% acetone to about 42 grams of potassium cyanide,then agitating and maintaining the temperature between 160 C. and 170C., venting to the atmosphere evolved gases. agitating after subsidenceof gasv evolution and maintaining the temperature at about 125 C. for aperiod of about one and one-half hours to two hours, cooling thereaction product, agitating the product with methyl alcohol and tanninin the proportions of 56.05 grams of 71.5% methyl alcohol and 0.03 gramsof tannin, and heating the mixture for about five hours between 93 C.and 95 C.

VINICIO DA VEIGA.

Name Date Macht Feb. 23, 1937 Number

1. THE STEPS OF HEATING IN A CLOSED VESSEL WITH 78 PARTS BY WEIGHT OFACETONE AND 42 PARTS BY WEIGHT OF CYANIDE OF POTASSIUM THE PRODUCT OFDIGESTING 2 PARTS OF TANNIN BY WIEGHT IN 150 PARTS BY WEIGHT OFCONCENTRATED SULPHURIC ACID, AND THEN ADDING SUFFICIENT TANNIN TORESTORE THE TANNIN TO THE AMOUNT ORIGINALLY PRESENT.